A fast, one pot, solvent-free and metal-free synthesis of poly-ε-caprolactone and poly(ethylene oxide) block copolymers is reported. Copolymers with different molar mass, different hydrophilic to lipophilic balance, high degree of conversion and narrow molar mass dispersity have been obtained by organocatalyzed ring opening polymerization of ε-caprolactone in presence of mono- or diol-poly(ethylene oxide) as initiator and fumaric acid as catalyst. A new biocompatible and environmental friendly purification method is presented, exploiting the upper critical solution temperature of these class of copolymers in ethanol. The phase diagrams of the synthesized copolymers in ethanol are also reported. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2992–2999.